EP0391271B2 - Wässriges hitzehärtbares überzugsmittel auf Polyester- und Acrylbasis, Verfahren zu dessen Herstellung und dessen Verwendung - Google Patents
Wässriges hitzehärtbares überzugsmittel auf Polyester- und Acrylbasis, Verfahren zu dessen Herstellung und dessen Verwendung Download PDFInfo
- Publication number
- EP0391271B2 EP0391271B2 EP90106124A EP90106124A EP0391271B2 EP 0391271 B2 EP0391271 B2 EP 0391271B2 EP 90106124 A EP90106124 A EP 90106124A EP 90106124 A EP90106124 A EP 90106124A EP 0391271 B2 EP0391271 B2 EP 0391271B2
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- EP
- European Patent Office
- Prior art keywords
- polyester oligomer
- water
- acrylate
- meth
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Definitions
- the invention relates the use of a aqueous thermosetting coating agent based on polyester and acrylic resin, in a mixture with amine resin and neutralizing agent, the usual Paint additives, pigments, fillers and / or organic Solvents can contain clear or colored single layers Decklecke in the production of multi-layer coatings in the Automotive industry.
- the structure of multi-layer coatings is special known in the automotive construction sector. It is it is cheap on a basecoat after a short drying time to apply a layer of clear lacquer "wet-on-wet", which is then burned in together.
- Aqueous basecoats are described in the literature and used in practice. Coatings of such Basecoats are still used in practice with non-aqueous Provide clear lacquer coatings.
- DE-PS 28 06 497 is a multi-coat paint with a Clear lacquer coating described as a top layer, this Clear varnish should also be water-thinnable; Examples for such water-borne clear coats, however not specified.
- Polyester is used as the basecoat coating agent with high molecular weight and high viscosity, dissolved in xylene, used, mixed with acrylic resins can be. Such varnishes have a high demand Neutralizing agents and give a when used high solvent emission.
- DE-OS 37 12 442 describes a mixture of polyester-melamine resin adduct with acrylic resins. Are here too high amounts of neutralizing agent necessary.
- EP-A-0 072 972 describes binders based on alkyd acrylates described, whereby the use of volatile amines should be avoided.
- the resins are made by acrylic polymerization in aqueous dispersions made from non-volatile amine neutralized alkyd resins; the dispersions obtained are again with non-volatile amines neutralized.
- DE-OS 36 32 617 describes aqueous coating compositions based on highly viscous resins, for example Polyester resins in which resin particles in which it can be acrylic resins are dispersed. The masses obtained are unstable and subject to one rapid phase separation.
- EP-A-0 206 072 describes film formers based on Acrylic polymer products described in a diluent made with a molecular weight above 200 were, among other things, a polyester can act. However, these film formers cannot be used in aqueous systems.
- the object of the invention is to provide of multi-layer coatings using colored Single-layer cover lick or clear varnish that a high Stability with low solvent content and less Have the amount of neutralizing agent.
- the polyester oligomer can be used to produce the polyester oligomer polyacrylate without solvent as the sole reaction medium be used.
- polyester oligomer polyacrylate but can also be compatible with water or in water added soluble solvent for the polyester oligomer become.
- Suitable solvents are preferably those which are unlimited are miscible with water.
- E.g. monovalent aliphatic Alcohols such as those with 2 to 4 carbon atoms, e.g. Ethanol and isopropanol or ketones, e.g. Acetone or Methyl ethyl ketone or glycol ether such as e.g. Methyglycol, Ethyl glycol, butoxyethanol, methoxypropanol, ethoxypropanol, and methoxypropxypropanol or diols such as e.g. Ethylene glycol and propylene glycol or polyether diols such as e.g.
- Polyethylene glycol and polypropylene glycol or any other people's water-miscible solvents Compound classes or the mixtures of the aforementioned Connections or connection classes.
- Proportionately Solvents are also used which are only limited or are not miscible with water at all in such amounts that it does not cloud the resin solutions or the varnishes made from it.
- the solvents or their mixtures have the task of resin solutions the waterborne paint compositions made entirely certain, among other things, necessary for later processing and give given properties.
- the coating agents used according to the invention have the advantage on that they have only small amounts of organic solvents contain. These small amounts are preferably by the for the production of the polyester oligomer polyacrylate used that during manufacture introduced or subsequently in the formulation of the Coating agents were added. Are particularly preferred aliphatic monoalcohols with 2 to 4 carbon atoms.
- the solvents contained in the coating agents are for example in amounts of 5 to 20% by weight on the ready-to-apply coating agent (containing Amine resin, polyester oligomer polyacrylate and additives, and optionally pigments, fillers, etc.).
- the solids content can the coating agent can be very high.
- clear, pigment and filler-free Compositions up to 50% solids available. They are stable in storage and can be used for the Application preferably with water to application viscosity be diluted.
- the low acid number also results the binder used the advantage of a low Need for neutralizing agents (e.g. amine), which in turn less inhibition when crosslinking with amine resins, e.g. Melamine resin, due to the low in the film remaining amine portion causes.
- neutralizing agents e.g. amine
- polyester oligomer-polyacrylate component of the binder as Polyester oligomers used in the reaction medium can be selected from those defined above Polyols, dicarboxylic acids and diols are produced.
- the starting materials are free from olefinic double bonds, so that the product obtained does not undergo radical polymerization can come in.
- the polycondensation is carried out according to the usual, the expert common processes, for example in the presence of usual esterification catalysts and at elevated temperatures from e.g. 180 to 230 ° C in the melt.
- examples for aliphatic triols and tetrols with 2 to 6 carbon atoms are trimethylolethane, Trimethylolpropane, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol and pentaerythritol.
- dicarboxylic acids examples include aliphatic saturated Dicarboxylic acids, e.g. Succinic acid, adipic acid, azelaic acid, Sebacic acid; cycloaliphatic saturated dicarboxylic acids and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, tetra-, Hexa-, endomethylenetetra-hydrophthalic acid, endoethylenetetrahydrophthalic acid and cyclohexanedicarboxylic acid (1.2, 1.3 and 1.4), muconic acid and camphoric acid, or possibly their possible anhydrides.
- Dicarboxylic acids e.g. Succinic acid, adipic acid, azelaic acid, Sebacic acid
- cycloaliphatic saturated dicarboxylic acids and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, tetra-, Hexa-, endomethylenetetra-hydrophthalic
- Examples of usable aliphatic diols are Ethylene glycol, propylene glycol (1.3 and 1.2), Butanediol, hexanediol (1.6), neopentyl glycol; and examples of cycloaliphatic diols 1,3-dimethylolcyclohexane and 1,4-dimethylolcyclohexane.
- polyester oligomer or its solution in one Monoalcohol become a hydroxy-functional (meth) acrylate ester, a monoethylenically unsaturated acid and / or a (meth) acrylic ester without hydroxy functions, either alone or in a mixture, a radical polymerization subjected in the presence of a radical initiator.
- radical initiators are:
- Dialkyl peroxides such as di-tert-butyl peroxide, di-cumyl peroxide;
- Diacyl peroxides such as di-benzoyl peroxide, di-lauroyl peroxide;
- Hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide;
- Peresters such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethylhexanoate, tert-butyl per-2-ethylhexanoate;
- Peroxidicarbonates such as di-2-ethylhexyl peroxydicarbonate, Dicyclohexyl peroxydicarbonate;
- Perketals such as 1,1-bis (tert-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cycl
- the polymerization initiators are generally described in an amount of 0.1 to 4% by weight, based on the weight of monomers, added.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monomers of component B) c) without functional groups are: (Meth) acrylic acid esters of alcohols with 1 to 12 carbon atoms in the chain, e.g. Methyl, ethyl, n-propyl, Isopropyl, butyl (n-, iso- and tert.-), hexyl, 2-ethylhexyl and lauryl alcohol, as well as aromatic vinyl compounds, such as styrene, vinyl toluene and ⁇ -methyl styrene.
- (Meth) acrylic acid esters of alcohols with 1 to 12 carbon atoms in the chain e.g. Methyl, ethyl, n-propyl, Isopropyl, butyl (n-, iso- and tert.-), hexyl, 2-ethylhexyl and lauryl alcohol, as well as aromatic vinyl
- Examples of the usable hydroxy-functional (meth) acrylic esters of component B) a) are (meth) acrylic esters of Ethylene glycol, propylene glycol (1.2 and 1.3), butanediols (1.4), hexanediols (1.6), and polyethylene glycol mono (meth) acrylate with 6 to 8 ethylene glycol units and n-propylene glycol mono (meth) acrylate with 5 to 6 propylene glycol units.
- Preferred examples are hydroxyalkyl (meth) acrylate lactone Adducts such as hydroxyethyl acrylate-caprolactone adducts, e.g.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acids component B) b) are acrylic acid or methacrylic acid as well as maleic acid and fumaric acid and their Half ester with aliphatic alcohols.
- the amine resin used as crosslinking agent in the coating composition according to the invention is any conventional amine resin crosslinking agent as used in the paint sector, provided that it is water-soluble or can be made water-soluble by adding organic solvents.
- the solvents are the water-compatible or water-soluble organic solvents described above for the production of the polyester oligomer polyacrylates and the production of the lacquers.
- water-soluble or, after addition of organic solvents, water-soluble amine resins are prepared by known processes (such as, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume 3, pages 475-496, 1953 and in Houben-Weyl, Methods of Organic Chemistry, volume 14/2 , Pages 319-388, 1963)) by reaction of aldehydes, in particular formaldehyde, with compounds bearing several amino or imino groups, such as melamine, urea, dicyandiamide and benzoguanamine, or mixtures of such products.
- melamine formaldehyde resins such as the commercial products Cymel 323 and 325, partially methylated melamine formaldehyde resins, such as the commercial products Cymel 373, 385 or highly methylolated melamine formaldehyde resins, such as the commercial products Cymel 300 and 301 (Cymel is a registered trademark).
- Such preferred melamine formaldehyde resins preferably contain the following functional groups
- the polyester oligomer polyacrylates are used to produce the coating agents subjected to neutralization with bases.
- the bases used are in particular those customary in the paint sector Amines, which are preferably volatile organic low molecular weight amines or ammonia acts.
- the polyester oligomer polyacrylate is neutralized, if necessary, with heating Achieving a favorable working viscosity or after Addition of water-compatible or water-soluble organic solvents.
- the base is in such a way Amount added to neutralize the pH of the obtained Product at about 7.0 to 10, preferably 7.5 to 9 lies.
- the neutralization can be carried out in the presence of the amine resin crosslinker as well as usual additives.
- Amine resin crosslinker and additives can, however, also after neutralization be added to the polyester oligomer polyacrylate.
- the neutralized product obtained is preferably after Addition of the amine resin crosslinker and other additives as well optionally solvents with water in such a Quantity added that one for storage and transportation suitable viscosity is obtained.
- Such a concentrate can then, for example, immediately before use with additional water, if necessary together with additional water Solvents diluted to the appropriate application viscosity become.
- the coating agents thus obtained have in the application state on the total weight of Water, solvent, amine resin, polyester oligomer polyacrylate and other additives such as pigments and Fillers etc. related solid content of up to 65% on. For clear coats that do not contain pigments or fillers contain, this solids content is, for example up to 50% by weight.
- the coating agents can be used as clear coats and formulated as a pigment or filler-containing paints become.
- Common additives are added to the formulation, such as leveling agents, deaerating agents, Dispersing aids, light stabilizers, anti-settling agents.
- pigments and fillers are added. These are around the usual in the paint sector depending on the application used inorganic and organic pigments as well as fillers.
- the coating agents can be used as clear lacquers be formulated. Clear varnishes of this type contain no pigments and Fillers. However, you can use conventional additives such as given above.
- the coating agents have excellent application technology Characteristics. They are therefore also for use as colored one-coat top coats suitable. A top coat with a clear coat not necessary.
- the coating agents can by conventional Application techniques are applied.
- the preferred Application technology is spraying.
- the spray order can be under Use conventional spraying techniques.
- the invention Coating agents can be in conventional layer thicknesses be applied. Surprisingly, it did shown that even with very thin layers of for example 20 ⁇ m optically perfect surfaces be achieved. It is also possible to use the Coating agents according to the invention also have high layer thicknesses to achieve.
- the manufactured Coatings are hardened by baking.
- Preferred Baking temperatures are around 130 to 160 ° Burn-in times between 15 and 30 minutes.
- Common curing catalysts can be used for this purpose be added.
- the coating agents are excellent suitable as aqueous clear coats, the in the automotive industry for multi-layer coatings find use as top coats. You stand out opposite the conventional organic solvent containing Systems particularly due to the low content of Solvents with high solids and lower Viscosity. Accordingly, they stand out a special environmental friendliness.
- the coating agents can be used as clear coats wet-on-wet on an aqueous or non-aqueous Basecoat to be applied.
- the wet-on-wet application includes drying the basecoat before application the clearcoat does not run out; hardening becomes common or the burn-in process is carried out.
- Binder films produced an equal height Property level like the known solvent-based Systems.
- Properties such as Surface hardness, clarity, Gloss, fullness, flow, scratch resistance, elasticity, Resistance to solvents, to care products, to certain chemicals, such as Brake fluid, diesel and Petrol, short and long-term weather resistance are the same as the known solvent-based ones Systems; some of them are also better.
- the coating agents according to the invention can can also be used as colored cover licks and too for this purpose, for example pigments, fillers etc., as is common in this sector.
- the binders contained in the coating agents show good pigment wetting ability, so that it is also possible is, the coating agent according to the invention as colored To use single-layer topcoats that are too glossy Coatings with excellent gloss retention and good mechanical technological properties.
- coating agents are used according to the invention, due to the low solvent content and the low need for neutralizing agents are particularly environmentally friendly. Due to the low proportion a small amount of neutralizing agents, such as amines Inhibition of crosslinking by melamine resins, whereby good mechanical and chemical resistance of the coatings obtained.
- the coatings show good weather resistance (they correspond to the latest requirements determined by the KFA test the edge filter test A, which is described in VDA test sheet 621-4, 3 point 2, July 1983).
- the coating agents have good storage stability as a lacquer.
- the proportion of organic solvents in the binders is low, which gives greater scope for solvent combinations in the paint formulation.
- mild solvents such as alcohols, such as ethanol, are possible.
- Good solvent release (including water) is thereby achieved, which enables rapid drying of the anat. The result is good process reliability.
- the low solvent content with high solids content and the use of water make environmentally friendly systems available.
- the product thus obtained has a stoving residue of 94.5% (1 h, 150 ° C), a viscosity of 3200 mPas (100%), a hydroxyl number of 466 and a color number of 30 Hazen.
- polyester oligomer from Example 1 717 g are mixed with 597 g Ethanol in a stirrer, reflux condenser, dropping funnel and thermometer equipped 4-liter three-necked flask Heated to reflux at 81 ° C.
- the product had a burn-in residue of 79.8% (1 h 150 ° C) at a viscosity of 7200 mPas (DIN 53015), an acid number of 26.3, an OH number of 231 and one Color number of 60 Hazen.
- the product had a burn-in residue of 84.0% (1 h 150 ° C) according to DIN 53182, a viscosity of 15830 mPas (DIN 53015), an acid number of 38.0 mg KOH / 1 g FK. (DIN 53402), an OH number of 231 mg KOH / 1 g FK. (DIN 53240) and a color number of 60 Hazen (DIN 53409).
- the paint had a viscosity of 31 seconds (measured in a DIN 4 cup at 20 ° C) and a pH of 9.0.
- the lacquer was drawn onto a glass plate using a wire doctor, predried at 80 ° for 15 minutes and baked at 140 ° C. for 20 minutes.
- the paint film obtained was clear and high-gloss and, with a layer thickness of 35 ⁇ m, had a pendulum hardness of 170 seconds, measured according to König.
- a lacquer film produced in the same way on a bare iron sheet (Erichsen sheet) had an Erichsen indentation of 6.3 mm. (HALS hindered amine light stabilizer)
- polyester oligomer polyacrylate according to Example 2 b 15.4 g butoxyethanol, 14.2 g dimethylethanolamine, 11.2 g a 75% solution of a defoamer of the type symmetrical acetylene glycols in ethylene glycol, 54.4 g demineralized water and 269.7 g of rutile-type titanium dioxide were listed one after the other in the specified order Laboratory dissolver mixed homogeneously and predispersed for 15 minutes and then on a laboratory bead mill from Type Drais PM 1 with ceramic beads with a diameter of 1.6 to 2.5 mm for 30 minutes at a temperature of 40 ° C grind.
- the paint concentrate obtained with 10.56 g of isopropanol, 10.56 g butoxyethanol and 55.1 g deionized water in one Viscosity of about 90 DIN seconds (measured in a DIN 4 cup diluted at 20 ° C). Before processing the paint by stirring in further demineralized water to a spray viscosity of 35 to 40 DIN-4 seconds (measured in the AK4 beaker at 20 ° C).
- Example 4 Basecoat was sprayed from a gravity cup gun in a layer thickness (measured after drying) from 25 to 30 ⁇ m on a with a cathodic dip primer and pre-treated with a stoving filler, zinc-phosphated iron sheet applied and 15 minutes predried at 85 ° C. Then the in Example 3b described water clearcoat after adding it of 14% by weight of a mixture consisting of 94% by weight demineralized water and 5 wt .-% butoxyethanol in one Spray viscosity of 35 DIN seconds (measured in AK4 cup at 20 ° C) was set with a Gravity cup gun applied in a layer thickness that after baking, a dry film thickness of approx.
- the paint film is highly scratch-resistant. The film will be 100 times by rubbing back and forth with one with methyl ethyl ketone impregnated felt. There is no swelling and no matting of the paint film.
- Example 2b 223.6 g of the binder named in Example 2b are mixed with 18.64 g Butoxyethanol, 9.2 g of a defoamer based on a symmetrical Acetylene glycol 75% dissolved in ethylene glycol, 0.8 g of an additive Avoiding surface defects Additol X W 329 (registered Trademark) and 18.64 g of dimethylethanolamine and added for 15 minutes touched. Then 24.8 g of fully demineralized water and 218.32 g Rutile-type titanium dioxide was added and another 15 minutes using a Dissolver pre-homogenized, let it rest for 24 hours and then with pearls on a "Drais PM 1" pearl mill for 30 minutes grind approx. 40 ° C.
- the paint is applied with a spray gun on a with a primer pretreated sheet metal applied in such an amount that after Burning in a lacquer film in a layer thickness of about 35 ⁇ m results.
- the painted sheet is left at room temperature for 10 minutes, pre-dries for another 10 minutes at 80 ° C and then burns for 20 minutes 140 ° C.
- the result is a high-gloss, highly scratch-resistant, flat lacquer film with a pendulum hardness (according to König) of 160 sec.
- the sheet is 240 hours subjected to the headlock test according to DIN 50017.
- the paint film shows this load no changes in gloss. There is no damage either such as bubbles, cracks, wrinkles and color changes occurred.
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Description
wobei die Monomeren a), b) und c) in derartigen Mengen eingesetzt werden, daß das erhaltene Polyesteroligomer-Polyacrylat eine Hydroxylzahl von 150 bis 390 und eine Säurezahl von 16 bis 40 aufweist, als Klarlacke oder farbige Einschichtdecklecke bei der Herstellung von Mehrschichtluckierungen in der Automobilindustrie.
Man legt 20 bis 50 Gewichtsteile eines hydroxyfunktionellen, radikalisch nicht polymerisierbaren Polyesteroligomeren, erhältlich aus den vorstehend definierten Diolen, Triolen und Tetrolen, sowie Dicarbonsäuren mit einem errechneten Molekulargewicht von 200 bis 1000, bevorzugt 300 bis 600, einer OH-Zahl von 280 bis 600, bevorzugt 400 bis 500, einer Säurezahl von 0 bis 1,5 vor und polymerisiert darin 80 bis 50 Gewichtsteile mindestens
in Anwesenheit eines Radikalinitiators.
- Mm
- = Mittleres Molekulargewicht
- W
- = Gewicht aller Komponenten abzüglich Kondensationswasser
- Mo
- = Anzahl aller Mole
- ea
- = Äquivalente der Säure
- W(AN)
- = Säurezahl des Polyesteroligomeren
Darüberhinaus sind milde Lösemittel, wie Alkohole, z.B. Ethanol möglich. Hierdurch wird eine gute Lösemittelabgabe (einschließlich Wasser) erzielt, wodurch eine rasche Anatrocknung ermöglicht wird. Es resultiert eine gute Ablaufsicherheit. Durch den geringen Lösemittelanteil bei hohem Feststoffgehalt sowie die Verwendung von Wasser werden umweltverträglich Systeme bereitgestellt.
(HALS = hindered amine light stabilisator)
Claims (8)
- Verwendung eines wäßrigen hitzehärtbaren Überzugsmittels auf Polyester- und Acrylharzbasis, im Gemisch mit Aminharz und Neutralisationsmittel, das übliche Lackzusatzstoffe, Pigmente , Füllstoffe und/oder organische Lösemittel enthalten kann, das
als Bindemittel enthältA) 20 - 45 Gew.-% (bezogen auf den Festkörpergehalt des Bindemittels) eines Aminharzvernetzers undB) 80 - 55 Gew.-% (bezogen auf den Festkörpergehalt des Bindemittels) eines nach Neutralisation mit Basen wasserlöslichen Polyesteroligomer-Polyacrylats mit einem Zahlenmittel des Molekulargewichts (Mn) von 800 bis 2000, hergestellt durch radikalische Polymerisation von 80 - 50 Gew.-% mindestensa) eines hydroxyfunktionellen (Meth)acrylsäureesters undb) einer monofunktionellen α,β-ethylinesch ungesättigten Carbonsäure undc) gegebenenfalls eines α,β-ethylenisch ungesättigten Monomeren ohne funktionelle Gruppen in 20 bis 50 Gew.-% eines hydroxyfunktionellen, radikalisch nicht polymerisierbaren Polyesteroligomeren, erhältlich durch Polykondensation ausschließlich von aliphatischen Diolen, cycloaliphatischen Diolen, Dicarbonsäuren und deren Derivaten, mit aliphatischen Triolen oder Tetrolen mit 2 mit 6 kohlenstoffatomen, mit einem errechneten Molekulargewicht von 200 bis 1000, einer Hydroxylzahl von 280 bis 600 und einer Säurezahl von 0 bis 1,5
wobei die Monomeren a), b) und c) in derartigen Mengen eingesetzt werden, daß das erhaltene Polyesteroligomer-Polyacrylat eine Hydroxylzahl von 150 bis 390 und eine Säurezahl von 16 bis 40 aufweist, als klarlacke oder farbige Einschichtdecklecke bei der Herstellung von Mehrschichtlackierungen in der Automobilindustrie. - Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß das Polyesteroligomer-Polyacrylat hergestellt wurde durch radikalische Polymerisation der Monomeren a), b) und c) in einer Lösung des Polyesteroligomeren in einem mit Wasser verträglichen bzw. in Wasser löslichen Lösemittels.
- Verwendung nach Anspruch 2, dadurch gekennzeichnet daß das wasserlösliche Lösemittel ein aliphatischer Monoalkohol mit 2 bis 4 Kohlenstoffatomen oder ein Glykolether ist.
- Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet daß der hydroxyfunktionelle (Meth)acrylsäureester der Komponente B) a) Polypropylenglykolmonomethacrylat, 4-Hydroxybutylacrylat oder ein Hydroxyethylacrylat-Caprolacton-Addukt ist.
- Verwendung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das überzugsmittel in Form eines Klarlacks ohne Pigmente und Füllstoffe vorliegt.
- Verfahren zur Herstellung eines wäßrigen hitzehärtbaren Überzugsmittels wie es in einem der vorhergehenden Ansprüche definiert wurde
dadurch gekennzeichnet, daß man 20 bis 50 Gew.-% eines hydroxyfunktionellen radikalisch nicht polymerisierbaren Polyesteroligomeren, erhältlich ausschließlich aus aliphatischen Diolen, cycloaliphatische Diolen, Dicarbonsäuren und deren Derivaten, mit aliphatischen Triolen oder Tetrolen mit 2 bis 6 kohlenstoffatomen, mit einem errechneten Molekulargewicht von 200 bis 1000, einer OH-Zahl von 280 bis 600, einer Säurezahl von 0 bis 1,5 vorlegt und in diesem Polyesteroligomeren 80 bis 50 Gew.-% mindestensa) eines hydroxyfunktionellen (Meth)acrylsäureesters undb) einer monofunktionellen α,β-ethylenisch ungesättigten Carbonsäure und gegebenenfallsc) eines (Meth)acrylsäureesters von Alkoholen mit 1 bis 12 Kohlenstoffatomen in der kette, in Anwesenheit eines Radikalinitiators polymerisiert, wobei die Monomeren a), b) und c) in derartigen Mengen eingesetzt werden, daß das erhaltene Polyesteroligomer-Polyacrylat eine OH-Zahl von 150 bis 390 und eine Säurezahl von 16 bis 40 aufweist,
worauf man 80 bis 55 Gewichtsteile des erhaltenen Polyesteroligomer-Polyacrylats mit 20 bis 45 Gewichtsteilen eines Aminharzvernetzers sowie gegebenenfalls mit üblichen Lackzusatzstoffen, Pigmenten, Füllstoffen und/oder organischen Lösemitteln vermischt. - Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die radikalische Polymerisation in dem Polyesteroligomeren gelöst in einem mit Wasser verträglichen oder in Wasser löslichen Lösemittel durchführt.
- Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß als mit Wasser mischbare Lösemittel ein aliphatischer Monoalkohol mit 2 bis 4 Kohlenstoffatomen verwendet wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3910829 | 1989-04-04 | ||
DE3910829A DE3910829A1 (de) | 1989-04-04 | 1989-04-04 | Waessriges hitzehaertbares ueberzugsmittel auf polyester- und acrylbasis, verfahren zu dessen herstellung und dessen verwendung |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0391271A2 EP0391271A2 (de) | 1990-10-10 |
EP0391271A3 EP0391271A3 (de) | 1991-10-02 |
EP0391271B1 EP0391271B1 (de) | 1994-12-14 |
EP0391271B2 true EP0391271B2 (de) | 2000-05-31 |
Family
ID=6377801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90106124A Expired - Lifetime EP0391271B2 (de) | 1989-04-04 | 1990-03-30 | Wässriges hitzehärtbares überzugsmittel auf Polyester- und Acrylbasis, Verfahren zu dessen Herstellung und dessen Verwendung |
Country Status (12)
Country | Link |
---|---|
US (1) | US5015688A (de) |
EP (1) | EP0391271B2 (de) |
JP (1) | JPH02292376A (de) |
KR (1) | KR970011343B1 (de) |
AT (1) | ATE115612T1 (de) |
AU (1) | AU637360B2 (de) |
BR (1) | BR9001566A (de) |
CA (1) | CA2013373A1 (de) |
DE (2) | DE3910829A1 (de) |
ES (1) | ES2068269T3 (de) |
MX (1) | MX172997B (de) |
YU (1) | YU65490A (de) |
Families Citing this family (30)
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DE4011633A1 (de) * | 1990-04-11 | 1991-10-17 | Herberts Gmbh | Verfahren zur herstellung von mehrschichtueberzuegen |
JPH05271614A (ja) * | 1992-01-29 | 1993-10-19 | Kansai Paint Co Ltd | 水性着色塗料組成物及びそれを用いる塗装方法 |
DE4209035A1 (de) * | 1992-03-20 | 1993-09-23 | Bayer Ag | Verfahren zur herstellung von hydroxyfunktionellen copolymerisaten |
DE4229196C2 (de) * | 1992-09-02 | 1995-02-23 | Herberts Gmbh | Pigmentpaste und deren Verwendung zur Pigmentierung von Überzugsmitteln |
DE4242518C2 (de) * | 1992-12-16 | 1996-10-02 | Bollig & Kemper | Wäßrige Polymerdispersionen für Klarlacke |
DE59405549D1 (de) * | 1993-01-13 | 1998-05-07 | Herberts Gmbh | Emulgatorfreies, hitzehärtbares Überzugsmittel, dessen Herstellung und Verwendung |
DE4317864A1 (de) * | 1993-05-28 | 1995-01-26 | Herberts Gmbh | Emulgatorfreies, hitzehärtbares Überzugsmittel, dessen Herstellung und Verwendung |
DE4317792A1 (de) * | 1993-05-28 | 1994-12-01 | Herberts Gmbh | Emulgatorfreies Überzugsmittel, dessen Herstellung und Verwendung |
DE4419216C1 (de) * | 1994-06-01 | 1995-08-31 | Bollig & Kemper | Wäßrige Überzugsmittel und deren Verwendung |
EP0769508B1 (de) * | 1994-07-07 | 2001-10-17 | Nippon Paint Co., Ltd. | Wasserdispergierbare harzzusammensetzung und verfahren zur herstellung derselben |
DE4427227A1 (de) * | 1994-08-01 | 1996-02-08 | Bayer Ag | Wäßrige Bindemittelkombination und ihre Verwendung |
DE4445200A1 (de) * | 1994-12-17 | 1996-06-20 | Herberts Gmbh | Wäßrige Überzugsmittel und deren Verwendung bei Verfahren zur Einschicht- und Mehrschichtlackierung |
DE19504015C2 (de) * | 1995-02-07 | 1998-08-13 | Bollig & Kemper | Mikrogel |
DE19512017C1 (de) * | 1995-03-31 | 1996-07-18 | Herberts Gmbh | Verfahren zur Mehrschichtlackierung |
DE19517277C2 (de) * | 1995-05-11 | 2000-11-09 | Herberts Gmbh | Verfahren zur Herstellung von Mehrschicht-Effektlackierungen |
DE19528878A1 (de) * | 1995-08-05 | 1997-02-06 | Herberts Gmbh | Wäßrige Überzugsmittel unter Verwendung von Polyalkylenglykoldialkylethern und Verfahren zur Mehrschichtlackierung |
US5773513A (en) * | 1996-04-04 | 1998-06-30 | E. I. Du Pont De Nemours And Company | Hydroxy functional acrylic polymer prepared via skew feed polymerization |
US5977256A (en) * | 1996-04-29 | 1999-11-02 | E.I. Du Pont De Nemours And Company | Scratch-resistant coating composition |
DE19625774A1 (de) * | 1996-06-27 | 1998-01-02 | Hoechst Ag | Selbstvernetzende wäßrige Dispersionen von Polyestern und Vinylpolymeren |
US5763528A (en) * | 1996-12-17 | 1998-06-09 | E. I. Du Pont De Nemours And Company | Coating compositions containing non-aqueous dispersed polymers having a high glass transition temperature |
WO1998045366A1 (en) * | 1997-04-09 | 1998-10-15 | Ashland Inc. | Thermoset cross-linkable pre-applied adhesive |
CA2296297A1 (en) | 1997-07-16 | 1999-01-28 | E.I. Du Pont De Nemours And Company | Graft copolymer emulsions and two-package waterborne urethane coatings |
AT405518B (de) * | 1997-08-07 | 1999-09-27 | Vianova Kunstharz Ag | Neue acrylatpolymerisate, deren grundlage polyesterharze oder polyester-oligomere sind, deren herstellung und verwendung in beschichtungsmitteln |
US6565978B1 (en) | 1998-02-18 | 2003-05-20 | Ppg Industries Ohio, Inc. | Multi-component composite coating composition and coated substrate |
US6270905B1 (en) | 1999-02-16 | 2001-08-07 | Ppg Industries Ohio, Inc. | Multi-component composite coating composition and coated substrate |
US6806302B2 (en) * | 2001-06-13 | 2004-10-19 | E. I. Du Pont De Nemours And Company | Process for the continuous production of liquid, pigmented coating compositions |
DE102004054499A1 (de) * | 2004-11-11 | 2006-05-18 | Bayer Materialscience Ag | Polyester-Polyacrylat-Dispersionen mit Reaktivverdünnern auf Basis von lactongruppenhaltigen Verbindungen |
DE102004054500A1 (de) * | 2004-11-11 | 2006-05-18 | Bayer Materialscience Ag | Polyester-Polyacrylat-Dispersionen mit Reaktivverdünner auf Basis von hydroxyfunktionellen Estern |
JP4634131B2 (ja) * | 2004-12-16 | 2011-02-16 | 関西ペイント株式会社 | アミノ樹脂水分散体組成物及び熱硬化性水性塗料組成物 |
CN101914345B (zh) * | 2010-08-30 | 2012-05-02 | 江苏荣昌化工有限公司 | 高装饰性聚酯—丙烯酸酯涂料 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE31985E (en) * | 1978-10-26 | 1985-09-17 | Dai Nippon Toryo Co, Ltd. | Aqueous dispersion type thermosetting coating composition |
DE3132937A1 (de) * | 1981-08-20 | 1983-03-03 | Henkel KGaA, 4000 Düsseldorf | Wasserverduennbare harzzubereitung auf basis von alkydharzen und polyacrylatharzen sowie deren verwendung als wasserverduennbare lackharze |
US4504609A (en) * | 1982-10-04 | 1985-03-12 | Nippon Paint Co., Ltd. | Aqueous coating composition |
JPH0635564B2 (ja) * | 1985-05-29 | 1994-05-11 | 日本ペイント株式会社 | 水性塗料組成物 |
US4681815A (en) * | 1986-04-16 | 1987-07-21 | E. I. Du Pont De Nemours And Company | Coating composition of polyester oligomer and acrylic binder |
JPH0699666B2 (ja) * | 1986-04-18 | 1994-12-07 | 日本ペイント株式会社 | 複合三次元化樹脂粒子ならびにその製法 |
US4740566A (en) * | 1986-05-23 | 1988-04-26 | E. I. Du Pont De Nemours And Company | High gloss color keyed guide coat |
DE3712442C2 (de) * | 1987-04-11 | 1996-12-12 | Alfred Krueger | Verwendung von sauren Polykondensaten zur Herstellung von wasserverdünnbaren Einbrennfüllern, Einbrenndecklacken und Einbrennklarlacken |
-
1989
- 1989-04-04 DE DE3910829A patent/DE3910829A1/de not_active Withdrawn
- 1989-10-26 US US07/427,460 patent/US5015688A/en not_active Expired - Lifetime
-
1990
- 1990-03-29 CA CA002013373A patent/CA2013373A1/en not_active Abandoned
- 1990-03-30 EP EP90106124A patent/EP0391271B2/de not_active Expired - Lifetime
- 1990-03-30 DE DE59007972T patent/DE59007972D1/de not_active Expired - Fee Related
- 1990-03-30 ES ES90106124T patent/ES2068269T3/es not_active Expired - Lifetime
- 1990-03-30 AT AT90106124T patent/ATE115612T1/de not_active IP Right Cessation
- 1990-04-03 AU AU52907/90A patent/AU637360B2/en not_active Ceased
- 1990-04-04 BR BR909001566A patent/BR9001566A/pt not_active Application Discontinuation
- 1990-04-04 MX MX020166A patent/MX172997B/es unknown
- 1990-04-04 JP JP2088424A patent/JPH02292376A/ja active Pending
- 1990-04-04 YU YU00654/90A patent/YU65490A/xx unknown
- 1990-04-04 KR KR1019900004654A patent/KR970011343B1/ko active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
KR970011343B1 (ko) | 1997-07-09 |
EP0391271A2 (de) | 1990-10-10 |
JPH02292376A (ja) | 1990-12-03 |
EP0391271A3 (de) | 1991-10-02 |
MX172997B (es) | 1994-01-27 |
DE3910829A1 (de) | 1990-10-11 |
ATE115612T1 (de) | 1994-12-15 |
ES2068269T3 (es) | 1995-04-16 |
CA2013373A1 (en) | 1990-10-04 |
AU5290790A (en) | 1990-10-11 |
AU637360B2 (en) | 1993-05-27 |
US5015688A (en) | 1991-05-14 |
EP0391271B1 (de) | 1994-12-14 |
KR900016400A (ko) | 1990-11-13 |
YU65490A (en) | 1991-08-31 |
BR9001566A (pt) | 1991-04-30 |
DE59007972D1 (de) | 1995-01-26 |
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